CN104744898A - Full-biodegradable film and preparation method thereof - Google Patents
Full-biodegradable film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composition of a high-tenacity full-biodegradable film and a preparation method thereof. The film is prepared from polylactic acid (PLA), poly propylene carbonate (PPC), polybutylene adipate terephthalate (PBAT) and a heat stabilizer. Blending modification sections are prepared by adopting a twin-screw extruder, blow molding is carried out by adopting a single-screw extruder, the prepared film has excellent tenacity and full biodegradable performance, and meanwhile the cost is low, so that the film is an ideal substitute for a current non-degradable film packing material.
Description
Technical field
The present invention relates to a kind of high tenacity full-biodegradable film composition and preparation method, be specifically related to a kind of full-biodegradable film prepared for raw material with poly (propylene carbonate) (PPC), poly(lactic acid) (PLA), poly-hexanodioic acid/mutual-phenenyl two acid bromide two alcohol ester (PBAT) and preparation method thereof.
Background technology
Plastic film packaging material, in daily life with in producing, play great function, but the currently used plastic film overwhelming majority is non-degradable or photodegradation product (polyethylene).The use of a large amount of thin-film material, causes a large amount of white pollution, brings a large amount of environmental problem, replaces current polyethylene product with biodegradable material, is the important means solving white pollution.
The full-biodegradable material of large-scale production has poly (propylene carbonate) (PPC), poly-succinic fourth diester (PBS), polytetramethylene glycol-succinic acid/hexanodioic acid copolyesters (PBSA), poly(lactic acid) (PLA), polycaprolactone (PCL), polyglycolic acid (PGA), poly-hexanodioic acid/butylene terephthalate (PBAT) and polyhydroxyalkanoate (PHA) (plastics science and technology up to now, 35 (7), 92 ~ 97,2007; Polyester industrial, 21 (3), 3 ~ 8,2008) etc., although but the material good film-forming property such as PBS, PBSA, PGA, PCL, price is higher, is difficult to accept for doing common packaging materials cost; PPC and PLA material price lower, but separately the film toughness of preparation is poor, cannot meet daily packaging needs.
It is the biodegradable composite material of raw material that Chinese Patent Application No. CN201210297866 discloses a kind of employing poly(lactic acid) (PLA), poly-hexanodioic acid/butylene terephthalate (PBAT) and treated starch, but when PBAT content is lower, still more crisp, when PBAT content is higher, better performances, but price is higher.
Summary of the invention
the object of the present invention is to provide a kind of full-biodegradable film and preparation method thereof, to solve the problems referred to above existing in prior art.
A kind of full-biodegradable film, it is made up of the following component counted by weight:
Poly-hexanodioic acid/butylene terephthalate: 35 ~ 80 parts;
Poly(lactic acid): 10 ~ 35 parts;
Poly (propylene carbonate): 10 ~ 35 parts;
Stablizer: 0.5 ~ 2 part.
The present invention adopts PBAT, PLA, PPC ternary blend systems, on the one hand, because PPC, PLA price is lower, the price of the finished product can be kept, on the other hand, PPC is higher due to molecular weight, can play the effect improving solution intensity and promote PLA and PBAT consistency, thus ensure the mechanical property of end article in modification and blown film process.
Preferably, described poly-hexanodioic acid/butylene terephthalate weight-average molecular weight is 30 ~ 200kDa, and molecular weight distribution is 1.5 ~ 4.When molecular weight is greater than 200kDa, price is higher, and when molecular weight is less than 30kDa, the strength of materials is poor, affects film performance.
Preferably, described poly(lactic acid) weight-average molecular weight is 30 ~ 300kDa, and molecular weight distribution is 1.5 ~ 5.When molecular weight is greater than 300kDa, materials processing temperature is higher, easily cause and be separated, affect film performance, when molecular weight is less than 30kDa, material is more crisp, affects film toughness.
Preferably, described poly (propylene carbonate) weight-average molecular weight is 400 ~ 900kDa, and molecular weight distribution is 2 ~ 6.5.Because poly (propylene carbonate) has higher molecular weight, melt viscosity is comparatively large, effectively can improve the stability of film bubble, and play compatibilization to poly-hexanodioic acid/butylene terephthalate and the blended of poly(lactic acid), thus improves the performance of film.
Preferably, described stablizer be stearic acid, oxidation inhibitor, antiaging agent, chainextender one or more.
A preparation method for full-biodegradable film as described in the present invention, it first adopts twin screw extruder to prepare the section of modification biological degradative resin, and adopt singe screw blowfilm shaping technique to prepare film packing material, detailed process is as follows:
---blended------dry---blow molding---packs in modification granulation to dry material.
Preferably, described concrete operations of drying material are:
Poly-hexanodioic acid/butylene terephthalate and poly(lactic acid) are dried to water-content lower than 100ppm under the drying conditions of 80 DEG C of air-flows, poly (propylene carbonate) is dried to volatile content lower than 300ppm under 40 DEG C of vacuum conditions.
Preferably, described blended select length-to-diameter ratio be 30 ~ 50 twin screw extruder, control each section of temperature at 90 ~ 220 DEG C.
Preferably, described blow molding length-to-diameter ratio is the single screw extrusion machine of 15 ~ 34, and controlling each section of temperature is 90 ~ 170 DEG C, and film blow-up ratio is 2 ~ 5:1, film thickness 6um ~ 50um.
Advantage of the present invention is that the film of preparation has excellent toughness and complete biodegradable, and also have lower cost, be the ideal substitute of existing non-degradable film packing material simultaneously.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not only confined to embodiment.
embodiment 1
PBAT: weight-average molecular weight 40kDa; Molecular weight distribution: 1.9 35 parts
PLA: weight-average molecular weight 110kDa; Molecular weight distribution: 2.2 35 parts
PPC: weight-average molecular weight 540kDa; Molecular weight distribution: 3.4 29 parts
Stablizer: stearic acid 1 part
Method: after raw material drying, adopt length-to-diameter ratio be 44 twin screw squeeze forcing machine granulation, after pellet drying, adopt length-to-diameter ratio be 18 single screw extrusion machine blown film, blow-up ratio 2.8:1, thickness 25um.
embodiment 2
Raw material:
PBAT: weight-average molecular weight 60kDa; Molecular weight distribution: 2.8 50 parts
PLA: weight-average molecular weight 170kDa; Molecular weight distribution: 3.3 25 parts
PPC: weight-average molecular weight 660kDa; Molecular weight distribution: 4.1 24 parts
Stablizer: stearic acid 1 part
Method: after raw material drying, adopt length-to-diameter ratio be 44 twin screw squeeze forcing machine granulation, after pellet drying, adopt length-to-diameter ratio be 18 single screw extrusion machine blown film, blow-up ratio 2.5:1, thickness 20um.
embodiment 3
Raw material:
PBAT: weight-average molecular weight 40kDa; Molecular weight distribution: 1.9 60 parts
PLA: weight-average molecular weight 170kDa; Molecular weight distribution: 3.3 20 parts
PPC: weight-average molecular weight 540kDa; Molecular weight distribution: 3.4 19 parts
Stablizer: stearic acid 1 part
Method: after raw material drying, adopt length-to-diameter ratio be 44 twin screw squeeze forcing machine granulation, after pellet drying, adopt length-to-diameter ratio be 18 single screw extrusion machine blown film, blow-up ratio 3:1, thickness 18um.
embodiment 4
Raw material:
PBAT: weight-average molecular weight 60kDa; Molecular weight distribution: 2.8 80 parts
PLA: weight-average molecular weight 110kDa; Molecular weight distribution: 2.2 30 parts
PPC: weight-average molecular weight 660kDa; Molecular weight distribution: 4.1 29 parts
Stablizer: stearic acid 1 part
Method: after raw material drying, employing length-to-diameter ratio is the twin screw extruder granulation of 44, and after pellet drying, employing length-to-diameter ratio is the single screw extrusion machine blown film of 18, blow-up ratio 4.2:1, thickness 8um.
embodiment 5
Raw material:
PBAT: weight-average molecular weight 60kDa; Molecular weight distribution: 2.8 50 parts
PLA: weight-average molecular weight 110kDa; Molecular weight distribution: 2.2 35 parts
PPC: weight-average molecular weight 540kDa; Molecular weight distribution: 3.4 14 parts
Stablizer: stearic acid 1 part
Method: after raw material drying, adopt length-to-diameter ratio be 44 twin screw squeeze forcing machine granulation, after pellet drying, adopt length-to-diameter ratio be 18 single screw extrusion machine blown film, blow-up ratio 2.8:1, thickness 50um.
embodiment 6
Raw material:
PBAT: weight-average molecular weight 60kDa; Molecular weight distribution: 2.8 60 parts
PLA: weight-average molecular weight 170kDa; Molecular weight distribution: 3.3 20 parts
PPC: weight-average molecular weight 660kDa; Molecular weight distribution: 4.1 19 parts
Stablizer: stearic acid 1 part
Method: after raw material drying, adopt length-to-diameter ratio be 44 twin screw squeeze forcing machine granulation, after pellet drying, adopt length-to-diameter ratio be 18 single screw extrusion machine blown film, blow-up ratio 3.5:1, thickness 25um.
embodiment 7
Raw material:
PBAT: weight-average molecular weight 60kDa; Molecular weight distribution: 2.8 60 parts
PLA: weight-average molecular weight 170kDa; Molecular weight distribution: 3.3 20 parts
PPC: weight-average molecular weight 660kDa; Molecular weight distribution: 4.1 19 parts
Stablizer: anti-oxidant 1 part
Method: after raw material drying, adopt length-to-diameter ratio be 44 twin screw squeeze forcing machine granulation, after pellet drying, adopt length-to-diameter ratio be 18 single screw extrusion machine blown film, blow-up ratio 3.5:1, thickness 25um.
embodiment 8
Raw material:
PBAT: weight-average molecular weight 60kDa; Molecular weight distribution: 2.8 50 parts
PLA: weight-average molecular weight 110kDa; Molecular weight distribution: 2.2 35 parts
PPC: weight-average molecular weight 540kDa; Molecular weight distribution: 3.4 14 parts
Stablizer: antiaging agent 2 parts
Method: after raw material drying, adopt length-to-diameter ratio be 44 twin screw squeeze forcing machine granulation, after pellet drying, adopt length-to-diameter ratio be 18 single screw extrusion machine blown film, blow-up ratio 2.8:1, thickness 50um.
embodiment 9
Raw material:
PBAT: weight-average molecular weight 60kDa; Molecular weight distribution: 2.8 80 parts
PLA: weight-average molecular weight 110kDa; Molecular weight distribution: 2.2 30 parts
PPC: weight-average molecular weight 660kDa; Molecular weight distribution: 4.1 29 parts
Stablizer: chainextender 0.5 part
Method: after raw material drying, employing length-to-diameter ratio is the twin screw extruder granulation of 44, and after pellet drying, employing length-to-diameter ratio is the single screw extrusion machine blown film of 18, blow-up ratio 4.2:1, thickness 8um.
comparative example
Raw material:
Low density polyethylene (LDPE)
Method: after raw material drying, adopt length-to-diameter ratio be 44 twin screw squeeze forcing machine granulation, after pellet drying, adopt length-to-diameter ratio be 18 single screw extrusion machine blown film, blow-up ratio 2.8:1, thickness 20um.
Film performance prepared by each embodiment and comparative example is in table 1
Table 1 film performance
As can be seen from Table 1, compare with common Low Density Polyethylene, the full-biodegradable film dart impact strength of same thickness improves more than 30%, and full-biodegradable film has excellent toughness.
Last it is noted that above embodiment only in order to illustrate the present invention and and unrestricted technical scheme described in the invention; Therefore, although this specification sheets with reference to each above-mentioned embodiment to present invention has been detailed description, those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent to replace; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in right of the present invention.
Claims (9)
1. a full-biodegradable film, is characterized in that, is made up of the following component counted by weight:
Poly-hexanodioic acid/butylene terephthalate: 35 ~ 80 parts;
Poly(lactic acid): 10 ~ 35 parts;
Poly (propylene carbonate): 10 ~ 35 parts;
Stablizer: 0.5 ~ 2 part.
2. full-biodegradable film according to claim 1, is characterized in that: described poly-hexanodioic acid/butylene terephthalate weight-average molecular weight is 30 ~ 200kDa, and molecular weight distribution is 1.5 ~ 4.
3. full-biodegradable film according to claim 1, is characterized in that: described poly(lactic acid) weight-average molecular weight is 30 ~ 300kDa, and molecular weight distribution is 1.5 ~ 5.
4. full-biodegradable film according to claim 1, is characterized in that: described poly (propylene carbonate) weight-average molecular weight is 400 ~ 900kDa, and molecular weight distribution is 2 ~ 6.5.
5. full-biodegradable film according to claim 1, is characterized in that: described stablizer be stearic acid, oxidation inhibitor, antiaging agent, chainextender one or more.
6. a preparation method for full-biodegradable film as claimed in claim 1, is characterized in that: adopt twin screw extruder to prepare the section of modification biological degradative resin, and adopt singe screw blowfilm shaping technique to prepare film packing material, detailed process is as follows:
---blended------dry---blow molding---packs in modification granulation to dry material.
7. preparation method according to claim 6, is characterized in that, described concrete operations of drying material are:
Poly-hexanodioic acid/butylene terephthalate and poly(lactic acid) are dried to water-content lower than 100ppm under the drying conditions of 80 DEG C of air-flows, poly (propylene carbonate) is dried to volatile content lower than 300ppm under 40 DEG C of vacuum conditions.
8. preparation method according to claim 6, is characterized in that, described blended select length-to-diameter ratio be 30 ~ 50 twin screw extruder, control each section of temperature at 90 ~ 220 DEG C.
9. preparation method according to claim 6, is characterized in that: described blow molding length-to-diameter ratio is the single screw extrusion machine of 15 ~ 34, and controlling each section of temperature is 90 ~ 170 DEG C, and film blow-up ratio is 2 ~ 5:1, film thickness 6um ~ 50um.
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